Patent GB-1026507-A (GB)
Title: Production of organo phosphorus compounds
IPC: C07F9/34
Filed: 1962-10-22
Abstract: Halogen atoms in trivalent phosphorus halide compounds which are phosphorus trihalides or trivalent organophosphosphorus halides are replaced by hydrocarbon or substituted hydrocarbon groups by reacting the said trivalent phosphorus halide compound with an organolead compound wherein the organo group is a hydrocarbon or substituted hydrocarbon group in the presence of a strong Lewis acid.  Also, halogen atoms in pentavalent phosphorus halide compounds which are phosphorus oxyhalides or thiohalides or pentavalent organophosphorus oxyhalides or thiohalides are replaced by hydrocarbon or substituted hydrocarbon groups by reacting the said pentavalent phosphorus halide compound with an organolead or organo-tin compound, wherein the organo group is a hydrocarbon or substituted hydrocarbon group, at elevated temperature or in the presence of a strong Lewis acid. Suitable strong Lewis acids are CuCl2, BeCl2, MgCl2, ZuCl2, CdCl2, HgCl2, boron halides, e.g. BF3 or BCl3, aluminium halides, e.g. AlCl3, AlBr3, AlI3 and GaCl3, InCl3, TlCl3, CeCl3, SuCl4, TiCl4, ZrCl4, SbCl4, BiCl5, BiCl3, TeCl2, TeCl4, MoCl4, WCl4, UCl4, FeCl2, FeCl3, CoCl2, CoCl3 and NiCl2, and also adducts formed with the desired end products, e.g. AlCl3 adducts with RPCl2, R2PCl and R3P wherein R is a hydrocarbon radical, and complexes of PCl3, a metal halide (strong Lewis acid) and a chlorohydrocarbon, e.g. the liquid complex [CH3PCl3+][Al2Cl7-].  Organic derivatives of the inorganic halides may also be used, e.g. C2H5AlCl2, (C2H5)2AlCl or C6H5AlCl2. The organo-lead compounds are preferably tetra-alkyl (cycloalkyl, aralkyl or aryl) lead compounds but tetra-unsaturated-hydrocarbyl lead compounds may also be used.  The hydrocarbon radicals may be substituted, e.g. by halogen, ester, ether, cyano or nitro groups, and trihydrocarbyl lead halides and dihydrocarbyl lead dihalides may also be used.  The organic trivalent phosphorus halide compound may contain one, two or more phosphorus halide groups and the phosphorus atoms can be linked directly or through a hydrocarbon group or hetero atom, e.g. O, S or N or may be a compound containing instead of or besides a hydrocarbon radical one or two radicals of ammonia or a primary or sec. amine, a hydroxyl compound or a mercaptan, or the radicals of a di-or polyfunctional-amine (including hydrazine, guanidine and urea), -alcohol, -phenol or -mercaptan.  The reaction with the organo-lead compound is preferably carried out in the absence of moisture and preferred reaction temperatures are 20 DEG to 120 DEG  C. Inert solvents, diluents or dispersing agents may be present and the starting phosphorus halide compound or the phosphorus compound to be prepared may be used as solvent.  In the reaction involving the use of the pentavalent phosphorus halides, the organic groups in the organo-lead and organo-tin compounds may be as defined above for the trivalent phosphorus halide reaction and according to the molar ratio of the reactants the products are phosphonyl halides, phosphinyl halides or tertiary phosphine oxides or their respective sulphur analogues. The starting phosphorus compounds include compounds composed of two phosphorus oxyhalide (or thiohalide) groups linked together through a hydrocarbon radical, an oxygen atom or a sulphur atom, e.g. Cl2P(O)-CH2-(O)PCl2, Cl(CH3)P(O)-CH2-(O)P(CH3)-Cl, Cl2P(O)-O-(O)PCl2, Cl(CH3)P(O)-O-(O)P(CH3)Cl and their possible sulphur analogues and also compounds containing radicals of hydroxyl compounds, mercaptans, ammonia or primary and sec. amines attached to P, e.g. CH3OPOCl2, (CH3O)2POCl, (CH3)2NPOCl2 and [(CH3)2N]2POCl and the possible sulphur analogues, and the compound <FORM:1026507/C2/1> Radicals of difunctional compounds, e.g. diols, dithiols, diamines, aminoalcohols or aminophenols may also be present on the phosphorus atom, and compounds in which P atoms are linked through one or two difunctional radicals, e.g. <FORM:1026507/C2/2> may also be used. When the process is carried out in the absence of a strong Lewis acid suitable temperatures are from 100 DEG  to 200 DEG  C.  The reaction may be carried out in the presence of a solvent and moisture is preferably excluded from the reaction mixture. When a strong Lewis acid is present external heating is not essential.  The pentavalent phosphorus halide compound is preferably one in which the halogen is chlorine but the fluorides, bromides and iodides may also be employed and specified organotin compounds which may be used are (CH3)3SnCl, (CH3)2SnCl, (CH3)2SnCl2, mixtures of (CH3)4Sn and SnCl4, tetraalkyltin, tetraphenyl tin and tetrabenzyl tin.  Several examples are given and the compound CH3PSCl2 which is obtainable by the defined process may be treated with ethyl alcohol in the presence of an HCl acceptor to form CH3P(S)Cl(OC2H5) which may then be reacted with HOCH2CH2CN in the presence of an HCl acceptor to give CH3P(S)(OC2H5)OC2H4CN which has insecticidal properties.